Efficient interfacial charge transfer of BiOCl-In2O3 step-scheme heterojunction for boosted photocatalytic degradation of ciprofloxacin

doi:10.1016/j.jmst.2021.12.070

Abstract

Abstract:

BiOCl as a representative layered bismuth-based photocatalyst with Sillén-structure has aroused wide public concern on photocatalytic degradation. However, the photocatalytic efficiency of pristine BiOCl is currently restricted by its low optical absorption and charge separation efficiency. Herein, step-scheme (S-scheme) heterojunctions of In₂O₃ nanoparticle and BiOCl micron-sheet were constructed by a convenient molten salt method by using a LiNO₃-KNO₃ system. The In₂O₃-BiOCl heterojunctions exhibit higher optical absorption performance from 380 nm to 700 nm than the pristine BiOCl and enhanced photocatalytic property toward ciprofloxacin (CIP) degradation under Xenon lamp illumination. The sample 20%In₂O₃-BiOCl showed the highest photodegradation efficiency, attaining 91% removal of CIP within 35 min, which was 39.6 times and 3.2 times higher than that of pristine In₂O₃ and BiOCl, respectively. The improved photodegradation property mainly resulted from the novel S-scheme mechanism, which boosted highly efficient separation of the photo-induced carriers. The photoluminescence spectrometric test and transient photocurrent response results demonstrated that In₂O₃-BiOCl composite exhibited efficient separation of photo-generated charge carriers. This work would provide new insights into the design of novel S-scheme photocatalytic systems with applicability in photocatalytic water treatment.

Key words: Step-scheme photocatalyst, In₂O₃, BiOCl, Photocatalytic activity, Ciprofloxacin

Kaiqiang Xu, Jie Shen, Shiying Zhang, Difa Xu, Xiaohua Chen. Efficient interfacial charge transfer of BiOCl-In₂O₃ step-scheme heterojunction for boosted photocatalytic degradation of ciprofloxacin[J]. J. Mater. Sci. Technol., 2022, 121: 236-244.

Figures/Tables 12

Fig. 1. XRD patterns of In2O3, BiOCl, 5%In2O3-BiOCl, 10%In2O3-BiOCl, 15%In2O3-BiOCl, 20%In2O3-BiOCl and 25%In2O3-BiOCl samples.

Fig. 2. SEM pictures of pristine BiOCl (a), In2O3 (b) and 20% In2O3-BiOCl (c), (d), TEM images of 20% In2O3-BiOCl (e), HRTEM image of 20% In2O3-BiOCl (f).

Table 1. Specific surface area and pore structure of prepared samples.

Sample	Specific Surface Area (m²/g)	Pore Volume (cm³/g)	Pore Diameter (nm)
BiOCl	0.92	0.004	22.05
In₂O₃	19.01	0.172	36.50
20%In₂O₃-BiOCl	2.29	0.011	24.90

Fig. 3. XPS spectra of prepared samples: high resolution spectra of Bi 4f (a), Cl 2p (b), In 3d (c) and O 1 s (d).

Fig. 4. DRS spectra of prepared samples (a) and corresponding Tauc plots (b).

Fig. 5. Mott-Schottky plots (a) and valance band XPS spectra (b) of BiOCl and In2O3.

Fig. 6. Photocatalytic activity of BiOCl, In2O3 and In2O3-BiOCl heterojunctions. The degradation rates of CIP for all samples in degradation percentage (a), kinetics of the CIP decomposition over different samples (b), the apparent rate constants k of the CIP decomposition over different samples (c) and temporal UV-Vis spectra of CIP solution for 20%In2O3-BiOCl (d).

Fig. 7. Recycling performance for CIP degradation of 20%In2O3-BiOCl (a) and effects of pH on CIP removal (b).

Fig. 8. Transient photocurrent responses (a), Nyquist plots (b), PL spectra (c) and EPR spectra of BiOCl, In2O3 and In2O3-BiOCl composites (d).

Fig. 9. ESR spectra of DMPO-•O2- (a) and DMPO-•OH (b) in an aqueous dispersion of BiOCl, In2O3 and 20%In2O3-BiOCl under 120 s of irradiation.

Fig. 10. Photocatalytic activities of the 20%In2O3-BiOCl for CIP degradation with disparate scavengers.

Fig. 11. S-scheme photocatalytic mechanism for In2O3-BiOCl nanocomposite under Xenon lamp irradiation.

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Efficient interfacial charge transfer of BiOCl-In₂O₃ step-scheme heterojunction for boosted photocatalytic degradation of ciprofloxacin

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